US2970125A

US2970125A - Method of preparing a stable oil extended latex

Info

Publication number: US2970125A
Application number: US602990A
Authority: US
Inventors: Bobbie H Smith; Thomas J Kennedy
Original assignee: Phillips Petroleum Co
Current assignee: Phillips Petroleum Co
Priority date: 1956-08-09
Filing date: 1956-08-09
Publication date: 1961-01-31
Anticipated expiration: 1978-01-31
Also published as: FR1180859A

Description

Jan. 31, 1961 B. H. SMITH ETAL METHOD OF PREPARING A STABLE OIL EXTENDED LATEX Filed Aug. 9, 1956 ACID-7 18 01 on. FEED ZONE IS/ l9 CAUSTIC I 7 EMULSIFYING wATER ZONE 20 Y CAUSTIC? OXIDANTY 4 s1 SOAP] ACTIVATOR 2 2| SMONOMEBS l MODIFIER 3 MIX ZONE V y POLYMERIZATION BLEND OILEX ZONE 1 ZONE 7' MONOMER MONOMERS REMOVAL ZONE 1.2

INVENTORS B. H, SMITH y T. J. KENNEDY difliculties have been encountered in producing stable oil-latex; emulsions.

2,970,125 METHGD or PRErARING A STABLE on.

Filed Aug. 9,1956, Ser. No. 502,990 9 Claims. (31. zen-23.7

This invention relates to oil extended rubbers. one of its aspects, this invention relates, to a method preparing a stable latex-oil emulsion.

The polymerization of monomeric material in aqueous emulsion is well known in the art, There are many activator recipes known to the art for preparing such latices. It is also known to use oil for extending rubbers by blending an oil emulsion with a latex. Such oil emulsions are especially useful in conjunction with those latices prepared from a recipe which would normally prodnce. a rubber having a relatively high ML-4 Mooney value. While such methods are well known to the art ,-certain preparing rubbers by such blends of oil emulsion and latex. When using the prior art blending methods, a part of the oil would separate from the blend and rise to the top of the latex after balling up and thereby fouling the tank, thus reguiring frequent cleaning. segregates in the coagulated for further processing.

By our invention, oil-latex Also, the separated'oil often rubber which is undesirable blends are produced which are stable and separation of the oil is prevented.

An object of this invention is to provide a method for Other objects, advantages and features of this invention will be obvious to those skilled in the art having been given this disclosure.

According to this invention, the oil-emulsion is prepared in the oil by partially neutralizing a soapforming acid, emulsifying the oil with the soap so formed and blending this emulsion with a latex having an excess amount of caustic in an amount sufficient to complete the neutralization.

We have found that when an oil emulsion having, an excess of acid is blended with a latex having an excess of caustic, the resulting latex-oil blend is stable as contrasted to the blending of an oil emulsion having all the acid neutralized with a latex. This is true even though the total ingredients are the same. While we can oflterno explanation for the improvement, we have foundthat by the prior art method of completely neutralizing the acid in the oil and blending with latex, the blending tank required cleaning about every 8 hours whereas,.surprisin'gly, when the acid is only partially neutralized in 'the oil with the remaining caustic being added to the latex and then blending, we can operate for about a month without cleaning the blending tank. This economic advantage is obtained in addition to the surprising result that theblend was stable and oil did not segregate prior to coagulation, thus resulting in a more uniform rubber crumb.

Polymerization recipes for forming latices of rubbery polymers are well known in the art (and any such recipe can be used. Examples of the more commonlyv used recipes include the iron pyrophosphate, diazothioether,

polyalkylene polyamine and the sulfoxylate recipes, all :known to the art.

In effecting such emulsion polymerization of monomeric -mate rial, particularly when a batch-type or lsemi batch C 2,970,125. Patented Jan. 31, 1961 2 type operation is carried out, the reactor is usaully first charged with the aqjueousmedium, which contains the desired'emulsifying agent, and the monomeric material is then added while agitating the contents. At the same time, a reaction modifier, such as a mercaptan, is also included, usually-in solution in at least a part of the monomeric material. An activator solution and an oxidant are separately added to the reaction mixture, and then the polymerization proceeds. The activator solution may be, and usually is, incorporated in the aqueous medium prior to the additionof themonomeric material, and then the oxidant is added as the last ingredient. Sometimes, however, satisfaetory polymerization results can be obtained when the-oxidant is incorporated prior to addition of the activator which is added as the lastingredient. It is also sometimesthe practice to add portions of. one or the other of the activator solution and oxidant intermittently or continuously, during the reaction. If thereaction is carried out continuously, streams of the various ingredients are admixed in somewhat the same order as they were in the hereinabove described .batch process prior to th ir final introduction into the poly- In u at o 2. .9. n th atex msste batshi s 9 pe en an .a method of preparing, such art.

Our invention, is applicable to latices of rubbery polymers. homopolymers or ,copolyrners preparing oil-extended These polymers can be the method of this However, these oil extended polymers are usually synthetic rubbers.

As hasbeen indicated, the emulsifier acid is usually oleic aczd ortall 011. However, otherfatty. and rosintacids amples ofother suitable rosin acids include dehydroaction between 'a strongbase and a Weak acid and for that reasonpthepl l of the emulsionwill be greater than 7 even when only suflicient alkali is used to stoichiometrically react with the acid. In general, when using a sodium hydroxide, a pH of about 11 of the emulsion would contain sufficient caustic to react with-all of the acid. We can use an oil in water emulsion of apH in the range of 8.4 to 9.5. The pH of the latex can be in the range of 11.0 to 11.5. In any case, sufficient causticshould be in the latex to neutralize the acid in the oil emulsion.

In general, the amount of oil per 100 parts of rubber will be dependent upon the nature of the copolymer and can vary from to 1000 parts oil per 100 parts rubber by weight but will' most generally be in, the range of 22.5 to 39.5 parts oil. per 100 parts rubber byweight.

The table below shows the preierredranges for this invention.

TABLE I H Oil-water emulsion: Range Parts water by weight 64-58 Parts oil by weight 35-40 Parts acid by weight l-l.3 Parts caustic by weight 0032-0125 pI-l 8.4-9.5 Equivalent caustic/acid ...21/l-.67/1 Latex:

Parts polymer by weight 16.0-21.5 Parts water by weight 84.0-78.5 Parts caustic 0.02-0.06 pH I 11-1l. 5

'Latex-oil-water emulsion: I

pl-I 9.5-10.5 Parts of oil/100 parts rubber by weightu 22.5-39.5

- As has been stated, the polymer useful in this invention can be homopolymers of conjugated dienes or copolymers of one or more conjugated dienes with a copolynierizable monomer. As those skilled in the art will understand, the conjugated diene most frequently used is l,3-'butadiene. However, other conjugated dienes can be employed. These conjugated dienes other than butadiene, which are generally preferred, are those which con. tain from four to eight, inclusive, carbon atoms per molecule and include isoprene (2-methyl-l,3-butadiene), piperylene, butadiene, chloroprene, and others. With a greater number of carbon atoms, the polymerization ratedecreases somewhat, and there are so many isomers that itis not practical, with present procedures, to provide pure compounds. However, in a broader aspect'ot the invention, conjugated dienes having more than 8, such as twelve, carbon atoms per molecule can be used, particuarly where the presence of various isomeric compounds can be tolerated. Furthermore, various alkoxy, such as methoxy and ethoxy, any cyano derivatives of these conjugated dienes, are also applicable. Thus, dienes, such as phenyl butadiene, 2,3-dimethyl 1,3 butadiene, 2 methoxy 3- ethyl-l,3-butadiene, 2-ethoxy-3-ethyl-l,B-hexadiene, 2- cyano-1,3-butadiene, and 2,3-diethyl-1,B-octadiene are applicable.

The copolymerizable monomers are well known in the art and include those containing an active CH -'-C group such as aryl olefins, heterocyclic nitrogen'monomers, esters of acrylic and substituted acrylic acids, nitriles, amides, ketones, ethers, and halides. Specific examples of such copolymerizable monomers include styrene, alpha-methyl styrene, various alkyl and substit'uted alkyl styrenes, vinyl pyridine, various alkyl and substituted alkyl vinyl pyridines, vinyl and alpha-methylvinyl quinolines, 3-phenyl-3-butene-l-ol, p-chlorostyrene, p-methoxystyrene, vinylnaphthalene, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate,

butyl methacrylate, methyl ethacrylate, acrylonitrile,

methacrylonitrile, methacrylamide, methyl isopropenyl ketone, methylvinyl ketone, methyl vinyl ether, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl furane, vinyl carbazole, vinyl acetylene and the like.

2-methyl-l,3-pentadiene, 2,3-dimethyl-L3- is then passed via conduit .Also added to this zone is water As has been previously said, the conjugated dienes will generally be'used in an amount of at least 50 weight percent in the polymerization recipe.

This invention will be further described in conjunction with the drawing which is a block flow diagram of one embodiment for the practice of this invention.

Referring now to the drawing, soap or emulsifier from conduit 1, activator from conduit 2, monomer from conduit 3 and modifier from conduit 4 are passed via conduit 5 to mix zone 6 wherein these ingredients are blended and emulsified. The resulting emulsion passes via conduit 7 to polymerization zone 8. At this same time, an oxidant is admitted to polymerization zone 8 via conduit 9. The latex formed in polymerization zone 8 passes via conduit 10 to' monomer removal zone 11 wherein unpolymerized monomer are recovered and returned to the polymerization zone via conduit 12. The monomer free latex leaves zone 11 via conduit 12 wherein caustic is added via conduit 14 to raise the pH to the desired level. The resulting high pH latex is then admitted to blend zone 14.

At the same time the latex is being prepared, an oil emulsion isprepared by passing oil via conduit 15 to oil feed tank 16. An emulsifying acid is admitted to the oil feed zone 16 via conduit 17. The resulting admixture 18 to emulsifying zone 19. via conduit 20 and caustic in amounts sufficient to completely neutralize the acid is emulsified with the soap formed by the reaction between the acid and caustic in zone 19. This emulsion then passes via conduit 21 to blending zone Example Several runs were made using a tall oil and ahighly aromatic oil to provide a 2.2 weight percent tall oil in aromatic oil mixture. A sodium hydroxide solution was added to this mixture and the material subjected to the action of a Waring blendor to produce a stable oil emulsion of the desired pH. A latex of an butadiene-l5 styrene copolymer prepared by a conventional ironpyrophosphate recipe (GR-S), having a pH of 9.4 was provided. Additional caustic was added as required. The latex and emulsion were blended using about 2 parts of oil per part of coplymer. The blend was tested by subjecting the blend to the action'of an electric mixer for one minute. The results are tabulated below.

From the above data, it can be seen that when the emulsion is substantially neutralized, the emulsion readily breaks down. Reducing the pH of the emulsion alone improves the stability of the blend. However, when the pH of the latex is raised sufficiently to complete the saponification (Mix C), the resulting latex is stable. We claim:

1. In a process of preparing a blend ota synthetic rubber latex prepared by emulsion polymerization of monomers comprising at least 50 weight percent conjugated diene the remaining monomer being a copolymerizable compound having a polymerizable ethylenic unsaturation and a petroleum oil emulsion prepared with sisting of fatty and rosin acids an alkali selected from the group consisting of sodium hydroxide and potassium hydroxide to the resulting oil acid mixture in an amount insuflicient to saponity all of the acid, emulsifying the oil in water with the saponified acid, adding additional alkali of the aforesaid type to the rubber latex in an amount when added to the first the unsaponified alkali is at least equivalent to said acid and thereafter blending the latex and oil emulsion thereby saponifying the remaining acid.

2. A process for preparing a stable blend of a synthetic rubber latex prepared by emulsion polymerization of monomers comprising at least 50 weight percent conjugated diene the remaining monomer being a copolymerizable compound having a polymerizable ethylenic unsaturation with a petroleum oil which comprises adding water and an acid selected from the group consaponifiable with an alkali to said oil, adding an alkali selected from the group consisting of sodium hydroxide and potassium hydroxide to the oil in an amount to supply 0.21 to 0.67 equivalent alkali per equivalent acid thereby saponifying only a portion of said acid, emulsifying the oil in the water in the presence of the saponified acid, adding additional alkali of the aforesaid type to the rubber latex in amount at least equivalent to the unsaponified acid and thereafter blending the latex and oil emulsion.

3. A process for preparing a stable blend of a synthetic rubber latex prepared by polymerizing a conjugated d.ene of 4 to 12 carbon atoms with a petroleum oil which comprises emulsifying said oil in water by adding to said oil an acid selected from the group consisting of fatty and rosin acids, saponifiable with an alkali adding an alkali selected from the group consisting of potassium hydroxide and sodium hydroxide and water to said oil and acid in an amount to supply 0.21 to 0.67 equivalent said alkali per equivalent said acid, thereby saponifying only a portion of said acid, and blending the mixture to form an emulsion, adding additional alkali selected from the group consisting of potassium hydroxide and sodium hydroxide to said latex in an amount when added to first said alkali to be at least equivalent to said acid, and blending the oil emulsion and the latex in an amount to provide 5 to 1000 weight parts oil per 100 parts rubber.

4. A process for preparing an oil extended rubber which comprises emulsion polymerization of monomers comprising at least 50 weight percent conjugated diene of 4 to 8 carbon atoms, the remaining monomers being selected from the group consisting of aryl olefins, heterocyclic nitrogen monomers, esters of acrylic and substituted acrylic acids, acrylic and substituted acrylic nitriles and amides, vinyl ketones, vinyl ethers, vinyl halides, vinyl furanes, vinyl carbazoles, and vinyl acetylenes; emulsifying a petroleum oil in water by adding to said oil and water an emulsifying acid selected from the group consisting of fatty and rosin acids saponificable with an alkali; adding an alkali selected from the group consisting of sodium hydroxide and potassium hydroxide to the resulting oil mixture in an amount to provide 0.21 to 0.67 equivalent alkali per equivalent acid thereby saponifying a portion of said acid; agitating the oil and water in the presence of the resulting soap to emulsify same; adding additional alkali of the aforesaid type to the latex in an amount when added to the first said alkali will provide at least equivalent alkali and acid; blending the latex with the oil emulsion in a ratio to provide 5 to 1000 weight parts of said oil per parts rubber and thereafter coagulating the polymer.

5. The process of claim 4 wherein the oil emulsion and latex are blended in a ratio to provide 28.5 to 39.5 weight parts oil per 100 parts rubber.

6. The process of claim 5 wherein the acid is tall oil.

7. The process of claim 6 wherein the latex is prepared by emulsion polymerization of butadiene-l,3 and styrene.

8. The process of claim 5 acid.

9. The process of claim 5 acid.

wherein the acid is oleic wherein the acid is rosin References Cited in the file of this patent UNITED STATES PATENTS Carter June 1, 1954 FOREIGN PATENTS Australia Aug. 18, 1953 OTHER REFERENCES India Rubber World, pp. 309-12, vol.

Claims

1. IN A PROCESS OF PREPARING A BLEND OF A SYNTHETIC RUBBER LATEX PREPARED BY EMULSION POLYMERIZATION OF MONOMERS COMPRISING AT LEAST 50 WEIGHT PERCENT CONJUGATED DIENE THE REMAINING MONOMER BEING A COPOLYMERIZABLE COMPOUND HAVING A POLYMERIZABLE ETHYLENIC UNSATURATION AND A PETROLEUM OIL EMULSION PREPARED WITH AN EMULSIFYING SOAP WHEREIN THE EMULSIFYING SOAP OF THE OIL EMULSION IS PREPARED IN SITU BY SAPONIFICATION OF AN ORGANIC ACID SAPONIFIABLE WITH AN ALKALI, THE IMPROVEMENT COMPRISING ADDING SAID ACID TO SAID OIL, ADDING AN ALKALI SELECTED FROM THE GROUP CONSISTING OF SODIUM HYDROXIDE AND POTASSIUM HYDROXIDE TO THE RESULTING OIL ACID MIXTURE IN AN AMOUNT INSUFFICIENT TO SAPONIFY ALL OF THE ACID, EMULSIFYING THE OIL IN WATER WITH THE SAPONIFIED ACID, ADDING ADDITIONAL ALKALI OF THE AFORESAID TYPE TO THE RUBBER LATEX IN AN AMOUNT WHEN ADDED TO THE FIRST THE UNSAPONIFIED ALKALI IS AT LEAST EQUIVALENT TO SAID ACID AND THEREAFTER BLENDING THE LATEX AND OIL EMULSION THEREBY SAPONIFYING THE REMAINING ACID.